Patent GB-1308811-A (GB)
Title: Triazine derivatives
IPC: C07D251/70
Filed: 1970-05-22
Abstract: 1308811 s-Triazine derivatives AMERICAN CYANAMID CO 22 May 1970 [22 May 1969 (3)] 24974/70 Heading C2C [Also in Division A5] Novel compounds of Formulµ (a) to (f) wherein R 1  is (C 1 -C 8 ) n-alkyl, (C 4 -C 8 ) secalkyl, (C 4 -C 11 ) tert-alkyl, (C 3 -C 8 ) cycloalkyl or methyl-substituted (C 3 -C 8 ) cycloalkyl; each of R 2  and R 3  is individually (C 4 -C 8 ) sec-alkyl, (C 4 -C 11 ) tert-alkyl, (C 3 -C 8 ) cycloalkyl or methyl-substituted (C 3 -C 8 ) cycloalkyl; R 4  is adamantyl or bicyclo [2.2.1]heptyl; each of R 5  and R 6  is individually (C 1 -C 8 ) n-alkyl, (C 4 -C 8 ) sec-alkyl, (C 4 -C 11 ) tert-alkyl, (C 3 -C 8 ) cycloalkyl, methyl-substituted (C 3 -C 8 ) cycloalkyl, adamantyl, bicyclo [2.2.1]heptyl or methylsubstituted bicyclo [2.2.1]heptyl; R 7  is (C 4 - C 11 ) tert-alkyl, adamantyl, methyl-substituted adamantyl, bicyclo [2.2.1]heptyl or methyl substituted bicyclo [2.2.1]heptyl; R 8  is (C 4 - C 8 ) sec-alkyl, (C 4 -C 11 ) tert-alkyl, (C 3 -C 8 ) cyclo-   alkyl, methyl-substituted (C 3 -C 8 ) cycloalkyl, adamantyl, methyl substituted adamantyl, bicyclo [2.2.1]heptyl or methyl-substituted bicyclo [2.2.1]heptyl; each of (R 9  and R 10 ) and (R 11  and R 12 ) are taken together with the nitrogen atom to which they are attached in each instance to form a polymethylene-imino group of from 4 to 6 carbon atoms substituted with from 0 to 4 methyl groups; R 13  is (C 1 -C 8 ) nalkyl, (C 4 -C 8 ) sec-alkyl, (C 3 -C 8 ) cycloalkyl or methyl substituted (C 3 -C 8 ) cycloalkyl; R 14  is (C 1 -C 8 ) n-alkyl or sec-alkyl; and R 15  is methyl substituted adamantyl provided that R 1 , R 2  and R 3  are not identical representing t-butyl, cyclohexyl or 2,4,4-trimethyl-2-pentyl-; or a non- toxic pharmaceutically acceptable salt thereof, are prepared by one of the following methods, (a) a compound of formula wherein each Z is individually chloro, bromo, fluoro, iodo, hydroxyl,-O-alkyl,-O-phenyl, -SH, -S-alkyl, -SO-alkyl, -SO 2 -alkyl- N 3 , -C#N, -N<SP>+</SP>(CH 3 ) 3 , -NH 2 , trichloroalkyl, trifluoroalkyl, guanidino, R-substituted guanidino, NHR or NRR; not more than two of the Z substituents being -NHR and/or -NRR; with a compound of the formula wherein X is -NH 2 , -CO-R, -CHO, -CR=CR, -NHY wherein Y is -CN, -NH 2 , -OH, acyl, sulphonyl, Si(CH 3 ) 3  or a negative charge; -Cl, -Br; F, -I, -OH, -O-alkyl, -O-phenyl, -SH, -S-alkyl, -SO-alkyl, -SO 2 -alkyl, -N 3 , -C#N, -N<SP>+</SP>(CH 3 ) 3 , -NH 2 , -NHR or -NRR; at least one of X and Z containing nitrogen, with the proviso that when X is the same group as Z, X and Z are either -NH 2  or -NHR; R in each case above being selected from R 1  to R 15  such that the compound produced by the reaction is a compound within any one of the Formulµ (a) to (f) above, or when X is -CO-R or CHO, the compound produced by the reaction is reducible to a compound within any one of the Formulµ (a) to (f) above; in the presence or absence of a Lewis acid catalyst in a stepwise manner when the R-substituents on the compound to be produced are different, or in a stepwise and/or concurrent manner when the R- substituents on the compound to be produced are the same; and when X is -CO-R or -CHO, reducing the resulting compound to a compound within any one of the Formulµ (a) to (f) above; (b) when the desired product is a tris-(alkyl-substituted amino)-s-triazine it may be prepared by trimerizing by heat treatment with alkali, a compound of the formula R-C#N; or (c) by reacting a compound of formula wherein Z is defined above, n is 1, 2 or 3 and A and B are chemical valencies which, when taken together form a single bond, or may be bonded to other atoms in a symmetrically or unsymmetrically substituted dimeric or trimeric open chain, with a compound of the formula wherein R and X are each as defined above and the selection of R, X and Z being subject to the same provisos as laid out hereinabove; in the presence or absence of a Lewis acid catalyst, and thereafter, or concurrently, cyclizing the compound produced, or being produced and, when the compound produced is in the form of an iso melamine, isomerizing the isomelamine into an s-triazine of any one of the Formulµ (a) to (f) by treatment with a base. Intermediates isolated in the above processes as exemplified are: 2,4-dichloro-6-(2,2,6,6-tetramethyl - 1 - piperidino) - s - triazine, 6 - chloro- 2,4 - biscyclohexylamino - s - triazine, 2- chloro - 4,6 - bis - (2,3,3 - trimethyl - 2 - butylamino) - s - triazine, 2 - cyano - 4,6 - bis - (2,4,4- trimethyl - 2 - pentylamino) - s - triazine, 2,4- bis - (N - acetyl - 2,4,4 - trimethyl - 2 - pentylamino) - 6 - (2,4,4 - trimethyl - 2 - pentylamino)- s - triazine, 2 - chloro - bis - (tert - pentylamino) - s - triazine, 2 - phenoxy - bis - (tertpentylamino) - s - triazine, 2 - methoxy - bis- (2,4,4 - trimethyl - 2 - pentylamino) - s - triazine and 2 - methylthio - 4,6 - bis - (2,4,4 - trimethyl- 2-pentylamino)-s-triazine. Reference has been directed by the Comptroller to Specification 1,013,223.